Method of making hydrogen



' ducing hydrogen.

. components of natural gas.

2,911,288 Patented Nov. 3', 1959 e f 1C@ I 2,911,288 i y t MEirHol') oFMAKING HYDRoGEN Prentiss S. Viles, Baytown, Tex., assigner, by me'sne'`assignments'yto EssoY Research and- Engineering f Company, Eliabeth,NJ., a corporation of Delaware "Application May 28, '1956, Serial No.587,566 11 Claims'. (cl. 234-212) Thepresent linvention isdirected to amethod for pro- More particularly, the invention is concerned withtheproduction `of hydrogen from hydrocarbons.` In its more specificaspects, the invention is directed to the production of hydrogen fromhydrocarbons in the presence of a mixture of` cobaltous oxide andmolybdic trioxide.

The present invention may be brietly described as in- .Volving the`production of hydrogen from, hydrocarbons by contacting Iahydrocarbonwith a mixture of cobaltous oxide andfmolybdictrioxide at a temperatureWithin the The'amount of steam employed whensteam isfincluded 1in thehydrocarbon feed may range downwardlyV from the theoretical' 'amountoffone molfof watery per mol of lcarbonpre'sent in therhydrocarbonfeed;l -sincethe addin are pure alpha and gamma alumina.

range from about 1.0 to25.0 weight percent with a preferred amount ofapproximately 15.0% by weight ofthe total catalyst.

The supports for `.the catalyst mixture may suitably be alumina,zirconia, magnesia, silica, silica-alumina, Filtrol,

kieselguhr, Floridan, and the like. kPreferred supports The temperaturesemployed in the vpractice of the pres-4 ent invention may suitably fallwithin the range of about 850 to about 1600o F. with a preferred'temperaturey range of 1 100 toabout 1400 F.` Quite satisfactory re#sults have been obtained at about 1300 F.

ALow pressures are desirable" iny the' practice of the pres'- entinvention. The pressures may range from aboutO pounds absolute to 'about1000 pounds per square inch gauge .with a preferred pressure" of aboutatmospheric. l vrThe 'feed stock may be contacted with the catalyst at asuitable feed rate which may be in the range from about 1 to about500'volun1es of feed per voluhie of catalyst per. hour with-a preferredv./v./hour.. from about 50 .toebout 100. The reaction may beconductedini either the vapor or liquid phase but vapor phase is to vdeposited onthe vcatalyst during thisl reaction and the I. catalyst retains itsvactivity in forming hydrogen and car# bon monoxide.

tion `ofmore vthan fthe'theoretical, would result in the VformationV ofsomeY undesired'carbondioxide. The preferred Vamount-fof-'added steam isone mol of. steam for .eachmol'ofi'carbon present inthellydrocarbonjeed. "It maywbe'ffstated that the' amount of steam employedmay vary 'downward'. from the theoretical dependingvon 1 theconcentration of carbon `monoxide desired'dn v the A product in therange from about 0.25 to about 1 mol of steam for each mol of carbon.

The feedhydrocarbon may be-a normally gaseous saturated-hydrocarbonhaving 1 to 3 carbon atomsin the molecule. Preferred feed stocks willinclude=methane, ethane, andpropane, natural gas, and vnormally gaseousIt will be desirable not to employ the C4, C5; and C6 hydrocarbons.

. equipment.

be preferred.

The-invention may beV practiced in various, tYPeS of For example, thereaction zone may have a catalyst bedY arrangedtherein as a xedbed Aorthe reaction may be conducted' in the so-called uridi'ze'd powdertechnique wherein thetcatalyst mixture is sus-` pended in vaporizedhydrocarbons'.l Furthermore, the reaction may be conducted in asuspension or in a slurry. `The present invention 4will be, furtherillustrated by reference to the drawings in which: v

Fig. 1 is a how diagram of a preferred mode; and Fig.' v2.-is` ak flowdiagram representingy another mode of practicing the invention.Referring now tothe drawingand particularly to Fig. l, numeral 11*designates a. chargeline throughyvhich a light hydrocarbon,. for.example.methane `or natural gas, may be. introduced intovthe. systemfrom asource vnot shown.4 Line 11-is.controlled suitablyby valvek 12 forreasons .which will be indicatedfurther` hereinafter. Under somesituations, it mayy be ,desirable toffadmix steam with. .theIfeed:hydrocarbon.and branch line 13 controlled 4by valve 14. isprovided. for that purpose. The hydrocarbon in linell passes into aheatertor` furnace 15 which may suitably be provided with gasburners 16wherein the hydrocarbon is heated` to a temperature withinv the rangeindicated in coil 17. It is to be noted thatline 11- is provided with asecond control valve 18 toallow bypassing of heater 15as may be desired.The heated hydrocarbon is discharged fromheater'lS by way of line 19 andthen may be introduced` by ybranch line 20 controlled by valve 21 into areaction zone, such as 22, which may be a plurality. of reaction zones.

Reaction zones 22 are provided with beds 23.01 catalyst mixturesupported on alumina, for example, for con- 'Ille catalyst employed inthe present invention isaA mixture of cobaltous oxide and "molybdictrioxide'preferably on a support. Within the purview of the presentinvention, thej catalyst is a'mixture of cobaltous oxide (CoO) andmolybdic trioxide (M003). Thecobaltous oxide and molybdic trioxide maybe employed in a preferred ratio of'mol per mol as the catalyst'but theratio'ofcobaltous oxide to molybdictrioxide may range from 0.-1:1'to120.1 mol of cobaltous oxide perfmol of Aducting the reaction. AOnpassage o`f the feed hydrocarbon into `contact with the bed 23 the feedhydrocarbon is substantially completely converted to hydrogen. This`product= is withdrawn from 'reaction zone 22 by way'of line 24controlled by valve-'25 and then vmay Ibe discharged by wayvv ofmanifold 26and1inev27 controlled by valve 28.- Since all of themethaneon hydrocarbon may not be converted in a single pass tohydrogen',it may be desirable.v to recycle all .or part of the product andlto thisend-:branchfline'29:controlled: by valve 3011s provided. Branch line29^connects linto line 31which',^in turn, connects into line 19.

l Suitably the hydrogen may be separated from the unconvertedhydrocarbon and provision is made to discharge at least a portion of theproduct in line 29 by way of line 32 controlled by valve 33 into aseparation zone 34 which suitably may be an adsorption zone. Inseparation zone 34 the hydrogen-containing gas is contacted with a solidadsorbent, which may be of the molecular sieve typeor any suitableadsorbent for hydrocarbons, introduced by line 35 into zone 34 such thatthe adsorbent contacts the hydrogen-containing gas counter-currently.Under the conditions prevailing in vzone 34, which suitably mayencompass temperatures in the range of 150 F. to 600 F. and pressuresfrom .15. to 500 p.s.i.g., the methane is selectively absorbed on theadsorbent while` the hydrogenremains unabsorbed and vis dischargedfrom'zone 34 by line 36. The eniiched'adsorbent is discharged from zone34 by line 37 and isl discharged therebyinto astripping zone 38`provided with a heating means illustrated by steam coil 39 foriadjustment of temperature and pressure. The stripped adsorbent is`discharged from zone 38 by line 35 and re-introduced into zone34 whilethe stripped methaney is removed overhead by line 40 controlled by valve41 and returned thereby to lineV 31 for re-use in the process. It may bedesirable to discharge part of the methane from the system and meanstherefor are provided by line 42, controlled by valve 43. The adsorbentmay suitably be employed as a fixed bed and mayv 'be stripped free ofadsorbed hydrocarbon by use of a suitable stripping gas readilyseparable from the methane. Other methods may be employed for purifyinghydrogen, such as described in Chemical Engineering Progress, September1955, pages 399 to 402, inclusive.

It is to be noted that two reactors 22 are provided. It is possible tooperate these two reactors in paralleler to employ one reactor while theother is undergoing regeneration to remove the carbon which is laid downon the catalyst mixture when the feed stock is only the hydrocarbon.This carbon may be removed from the catalyst by cutting out thehydrocarbon feed by closing valve 12 and allowing steam only to contactthe catalyst mixture in either of the reaction zones by opening valvev14 in line 13. Of course, it is to be understood that for economys sakeit will be desirable to operate the other reactor while the fouledreactor is undergoing regeneration and separate lines will have to beprovided to con- -duct such operations; For simplicitys sake these lines4are -not shown but it is to be clearly understood that such lines wouldordinarily beprovided.

In operating the'mode of Fig'. 1 where steam and hydrocarbon form thefeed stock, valve 14 in line 13 and valve 12 in line 11 would both beopen to form the desirable mixture of steam and hydrocarbon. Under theseconditions, the product rather than being substantially hydrogen orunconverted feed hydrocarbon will be substantiallyhydrogen and carbonmonoxide. This product may suitably be withdrawn by opening valve 28 inline 27.- A suitable use for this product is as a feed gas for theFischer-Tropsch synthesis of hydrocarbons or as va feed gas to theso-called oxo process.

It may be desirable under some conditions to bypass .'theheater 15 -atleast in part with the feed stock. Provision is, therefore, made tobypass either all or partiof the hydrogen' and/or steam from line 11 toline 19 by lwayofbranch line 44 controlled by valve 45.V Such bypassingmay suitably be done to provide a control of temperatures to thereaction zones 22.

u While an adsorptionl zone 34l has been shown as a means for separtinghydrogen from methane,it is to be understood that adsorption zone 34 maybe a fractional distillation zone, a combination of adsorption andcompression zones andany separation means by way of which hydrogen maybe separated from methane as desired. Adsorption zone 34 is shown merelyfor ,illustraill Pur' f regeneration zone i are provided for Vconductingthe reaction. Reaction zone 50 has a feed line 52 leading theretocontrolled by valve 53 by way of which natural gas or other hydrocarbonfeed stock is introduced. A heat exchanger 54 is provided in line 52 forheating the natural gas to reaction` temperature. The heated naturai gasis then introduced into inlet line 55- wherein it is admixed withregenerated catalyst mixture introduced thereby by line 56 controlled byvalve 57. In reaction zone 50 which may suitably operate at atemperature of approximately l300` F. and a pressure of 25 p.s.i.g., thenatural gas components are convertedV substantially 'completely tohydrogen. The reaction takes place principally in a dense bed indicatedby the shaded portion 58 and the hydrogen and unreacted hydrocarbon areseparated from the catalyst mixture in a suitable separation zone, suchasV 59, which may be a plurality of cyclone separators arranged in theupper portion of the reaction zone 50. Separation zone 59 is providedwith a dip leg 60 by wa'y of which the catalyst mixture is returned tothe dense bed 58. The separated hydrogen from separation zone 59 isdischarged Vby line 61 and passes in heat exchange with the feed gasthrough heat exchanger 54 to allow preheating the natural gas feed.

The catalyst from dense bed 58 drops into the lower part of reactionzone 50 and is withdrawn therefrom by line 62 and discharged into `astripping zone 63 provided with an inlet line 64 by way of which astripping gas, such as steam, may be introduced to remove volatilebodies from the catalyst mixture. This volatile material is introducedby line 65 into zone 51. The stripped catalyst mixture discharges byline 66 controlled by valve 67 into' regeneration zone 51 wherein acombustion reaction takes place by means of a .free oxygen-.containinggas introduced thereto by line 68 containing a blower 69. Temperatureconditions in zone 51 may suitably range from about `1l00 F. to .1800 F.and pressures from about 0 to about 750 p.s.i.g. A suitable temperaturein zone Slamay be approximately l400 F. and .a suitable pressure may beabout 25 p.s.i.g. Subatmospheric pressures may be suitable. .Thecombustion reaction in zone 51 causes carbonaceous bodies to be removedby combustion from the catalyst mixture and results in the formation oftue gas which is withdrawn from zone 51 by line 70. The regeneratedcatalyst mixture Viows into a funnel-shapedm'ember 71 which connects byline 72 to line 56 for return to reaction zone 50 as has been described.

The hydrogen after passage through heat exchanger 54 passies through acooler 73, thence through a trap 74 andra filter'75 to remove any solidparticles which may have been entrained with the hydrogen. The hydrogenis then withdrawn by line 76 and may be suitably used as a supply ofhydrogen in thermalj lor catalytic operations'frequiring a supply ofhydrogen. As typical of such operations may be mentioned hydrogenation,hydr'odesulfurization, hydrocracking, hydrodealkylationand the like.Many operations requiring hydrogen will suggest themselves to theskilled workman.

In order to illustrate the practice of the invention further, runs havebeen made in which a substantially methane feed stock was contacted withcobalt molybdate at 1300* to show the yields obtainable from feed stocksof nature. The catalyst employed was cata- 1 6 lyst mixturesupported'o'n alumina. Theresults'ofthese the hydrogenl contained'substantial amounts of'methaneY runs are shown in Table Ii which`will'frequire recycling to the.' operation. AthigherV TABLE I ChargeGas, Run Charge Emuent Hydrogen Total Volume, Length, Gas E'Iemp.,Pressure, Gas, Produced,

Llters Hrs. Rate, F. p.s.i.g. Total Total V./V./H.r. Volumes Volumes 248. 1,300. Atmospheric.- 33 27.4 3 37 1, 300 Atmospheric 30 26. 6 1 841, 300 200 16 6. s 1 e3 1, 300 200 10 6. s

Itv will' b`e" seen from anY examination of` the dataf in temperature,however;` at thev charged` gas rate the pro- Table I that substantialquantitiesof hydrogen were propane Was substantially completelyconverted to hydroduced from the feed stock. The results here appearmore gen. desirable at atmospheric pressure than at the higher pres-Additional runs were made with a substantially pure sure. methane feedstock at varying4 temperatures toi illustrate The analyses of theproducts recovered from: the runs effective temperatures. in theproduction of pure 'hydroshown in Table I are produced in Table II: gen.Pressures were atmospheric and the catalystfmixf ture was supported onalumina. The results offthese TABLE II operations are-shown 1n Table IV:

l lProduct Gas Froru i Charge Gas TABLE" IV Hydrogen 0.30 i 83.00 Y 74.048.00 43.00 25 Sample... Charge Product Product Product Methane.-. 99.0215.00 5 51.00 55.10 Gas Gas Ges. rvGas Ethylene 0. 02 0. 01 0. 01 0. 011 Ftlmnp 0. 5U 0. 02 Propylene 0. 10 0. 04 Reaction'Temperature; FPropane 0. 06 0. 05 Mol percent: Isobntsmo .06 Hydrogen.. 11BntaneMethane. EmtyleneeY Ethylene T nppnmrta Ethane n-Pentane' I Ptopylen'ePentylenes Propane. Cyclopentane and Heavler.- Isobutane n-Butane...Butylenes Column 2 1s the product from the run of two hours dura'-'sopmfm 1 11Pent8118 tron, whereas columns 3, 4 and 5 are the analysesfrom Pentylenes the product o f the otherruns' of three', one' andone-half CY1PenFanefand*Heavlefhours"durationgrespectively; It will beseen that the product`v from the runs ot twoland three hours duration Itwil-l beA seen fromv the. analyses presented 1n. Table IV n'npfises` amajor amount. of hydrogen and minor 40 that best TCSUIS Wel' Obtained at130 F.,. the plOdllCl amounts ofthe feed stock and`I other hydrocarbons.It bemg substantially completely Pure hydrogen- At lower willY be notedfront the data` in Table II-t-hat1therunS temperatures of apprxlmately1100 FLV the hydrogen atf the" higher pressure had decreasing: amountsofhydroe WaS I1= a minor amount indicating. thenecessity for gen. It isto be understood that when operating' at the recychng. f higherpressures within the range indicated, it may be In O I'del t0 ShOW theeffect 0f Va1'y 1ng the PfeSSUfe, desirable to recycle the product toinsure the production OpefalOIlS Were COIldUCted al atmospheflc and 200ILS-Lgof a major amount of hydrogen in the product. 5 pressure employingsubstantially pure methane as the feed Other operations were conductedwitha catalyst mix- SOCk These data are ShOWn 1n Table Vr ture supportedon alumina with methane, ethane and pro- TABLE V pane with temperaturesof 1300 F. for methane, ethane 50 and propane in one instance and atemperature of 15'5'0.q Gas analyses F. for the propane in the secondinstance. Pressures were atmospheric. The results of ltheseoperations-are sl'rownA chargeant-; Methane Methane Methane Methane inTable III- Charge Rate, V./V./Hr.. 80 80 20o Y Reactor Pressurem...Atmos- 200 200 TABLE III phen'c p'.s.i.g. p;s'.i.g.

' Sample; Chargev .Product Product. Product Product gas analyses Gas GasGas Gas Y v Mol percent: v Charge Gas Methane. Ethane `Propane` Propane.Hydrogen 0 M 79 5L 73 4 25 l/Itehlane. 93.3 4.81 47.68 52. s0 Charge GasRate v.;v./Hr a0 s0 Y. s0 yen@ Temperature, F 1,300 1,300 V1,300 gmane0-11 0- 01 0- 13 M01 Percent: ropylene 0.02 0 14 0. 16 0. 16 Hydrogen43. 46 Propane- 0. 04 0 05 0. 04 0. 02 Methane 49 28 3 Isobutane-. 0.02v0. 04. Ethy1ene"` i 2 62 n-Butane.- 0.- 02.- o. 01. .0.02 0. 04 Ethane'1 6 yButyleues 0.031 0.031 0:04 f 0.10 Propylegj 0 g3 Isopentnm 0:05f0. 09 Propane 1'91 n- Pentane 0: 02 0 22 0 20. 0.26 Ienhnmn'p"euy1enets..- 0.02 0.01 0. 02 n-Butane o 11 0.07 0. 04 Y Open an@ an eav1 Butylpnpq 0 03 191 0.05 0.05y 0.06

Isf)pe1.} tane 1 .en 1 .0 t npentylgees m 0.02 0 01; 70 It; will be seenthat Va constant charge" rate of 80 Cyclopentwend Heavler- 0.06 0.05v./v./hr. atk atmospheric pressurejg've's thev best. results,

the temperature in both instances being 11300a F. At It will be clearfrom the data in Table III that with higher charge rates at 200 p.s.i.g.pressure the hydrogen methane and ethane at 1300 F. substantially purehyproduction was affected adversely.

drogen was obtained, whereas with propane at 1300 F. 75 Additional runswere made to illustrate the effect of varying` charge gas rates and tothis end runs were made ofVVA a substantially pure methane at atemperature of 1300 F. and atmospheric pressure employing catalystmixture supported on alumina as a catalyst. The results where theproduct was obtained after varying times ofY use of the regeneratedcatalyst:` Y

of runs at varying charge rates are shown in Table VI:

TABLE VII TABLE VI Product gas analys'es I 10 Product gas analyses 1After After-Two Charge Threeand One- After After After After After GasFoul'th Fourth Sample Charge Total Total Total Total Total H0111' HOUISGas oil of1.5 of2 of4 1- oHf4.75

Hour Hours Emi-Irs Hours oms Total Volume Product Gas,Liters MolPercent: ChargeGasjRate, y Hydrogen v./v. 0 s0 150 240 s0 240 Methane--Mol Percent *l i Y Ethylene 07.5 s4. 00 72.10 90.10 j 58.80 Emana-- 1.415.50 27.50 9.50 30.10 Pfopyn 0.3 0. 01 V0.04 Y0. 02 0.05 20 Propane-0.5 0.08 0.01 0. 01 sobutall 0 02 n-Butane 0.12. Butylene 0.01 YIsopentau 1}13Btu11ane 0.11 ggg 0.05 0.07 Ilgelllftgflggs 3- nes.-.Isldpiitane-- 0.03 0.15 0.05 0.15 0.15 0 14 25 Cyclopentane and Her-vier0.04 n Pn'nfanA O. O2 0. 04 0. 10 Y Pentylenes 0.02 0.05 0.02 0.01 0.04Cyclopentane and Heavier.. 0.04 0.05 0.05 0.04

It will be seen from the data in Table VII wherein l the results ofthese runs are presented that regeneration Consldermg the Qta m Table VI1i Will be Seen that does not affect the catalytic activity of thecatalyst in best rsulltls are ltlvbtaei at alcharge1 gas ratebof aboutYproducing hydrogen from hydrocarbons y y ,A il? rhat Qug teslrab e msuts are. o. tamed at In order 'to show that the catalyst mixture is adesirable e g er c arge gas ra es' catalyst inthe practice of thepresent invention, runs In order to show the eiect of regenerating mecata- Were made wherein the catal lst of the' resent invention lystmixture after deposition of carbon thereon in the W d .th th yrt .edthp. xf ts f production of hydrogen in accordance with the present has.compare W1 al e SPPO al mpiiep alo invention, catalysts Which have beenregenerated by t e supported Cat yst muture' ompalfisons are so burningwere reused in the production of hydrogen em 40 made with othercatalysts to show the unexpected 1mploying a temperature of 1300 F.atmospheric pressure pfovement eiectef 111 the. Pfacfl Qf the Present1I1V11 and a charge gas rate of 26 v./v./hr. This catalyst was UQU- T116'data 111 Table VIH Which fOllOWS WaS 0bregenerated catalyst mixturesupported on gamma alutamed with natural gas as a feed stock at atemperature mina. The data from the operations are presented in of 1300F., atmospheric pressure and a charge gas rate Table VII whereinanalyses of the product are given of 60 v./v./hr.: f

TABLE VIII Gas analyses (mass spectrometer) {Operating conditions:Charge gas-natural gas from utility system; pressure-atmospheric; chargeratev./v.lhr.; catalyst-as indicated] Sample Clarge Product Gas ProductGas Product Gas Product Gas Product Gas Product Gas Product Gas asReaction Temp., F 1,300 1,300 1,300 1,300 1,300 1,300 1,300 CatalystUsed Catalyst Mix- Gamma A111- Molybdic Pure Cobalt Iron Oxide CobaltOxide Silica.-

ture on mina Support Oxide Sup- Oxide Type Supported Alumina Gamma Usedfor cataported on Without Catalyst on Alpha Cracking Alumina lystMixture Alumina Support Alumina Catalyst Mol Percent:

Hydrogen 94. 21 36. 79 40. 77 60. 20 1. 06 39. 33 5. 17 Met ane.- 5. 6163. 07 58. 36 39. 15 97. 27 60. 15 93. 78 Ethylene- O. 02 0. 01 0. 14 0.04 0. 21 0. 21 0. 15 Ethane 0. 03 0.03 0.03 0. 28 1. 31 0. l2 0. 06Propylene. 0. 08 0. 01 0. 01 0.03 0. 24 Propane 0. 43 0. 02 0. 08 0. 120. 01 Isobutane 0. 01 0. 08 n-Butane 0. 04 0. 05 0. 01 0. 10 0. 07 0. 050. 06 Butylenes 0. 01 0. 03 Isonnntmm 0. 03 0. 02 0. 11 n-Pentane 0. 090. 01 0. 30 0. 13 0. 24 Pentylenes- 0. 02 0. 01 0. 05 0. 01 Oyclopentaneand Heavier.-. 0.21 0.08 0. 05 0. 06

ItA will be seen from vTable VIII that in employing the catalystof thepresent invention very desirable results are obtainedLwhereasxth supportfor the catalyst does not give good results. Again comparing thecatalyst of the present invention with the components thereof,speciically molybdic oxide' and cobaltous oxide, it will be clear that asynergistic result is obtained by employing catalyst mixture rather thanmolybdic trioxide or cobaltous oxide alone. Also it is to be noted thatthe present invention gives vastly superior results over other catalystsunder the same conditions; for example, iron oxide does not effectivelyconvert and silica-alumina is also substa'h'tally ineffective. Fromthese data, it may be concluded that a mixture of cobaltous oxide andmolybdic trioxide, termed herein as catalyst mixture, gives asynergistic result in the production of hydrogen from methane.

In order to illustrate the production of a mixture of hydrogen andcarbon monoxide, runswere made with a dry natural gas from a commercialutility system and with the natural gas plus 3 mol percent of watervapor added thereto. These operations were conducted at a temperature of1300 F., at atmospheric pressure and at a charge gas rate of 60 volumesof gas per volume of catalyst mixture per hour.

The data in the following Table IX shows the hydrocarbon and carbonoxide analyses of the feed gas and the production gas from the two runs:

TABLE IX Product Gas from Natural Gas plus 3 percent Water Vapor NaturalGas from Utility System Product Gas from Charging Dry Natural Gas GasSample Mol. percent:

Carbon Dioxide Carbon .Monoxide Butylenes Pentylenes Cyclo Cs andHeavier It -will be noted from the data in Table 1X that where watervapor was not present substantially pure hydrogen was produced, but whenwater vapor was'added hydrogen in a major amount and carbon monoxidewere produced with minor and insignicant amounts of carbon dioxide andhydrocarbons. These data show 'that both hydrogen and carbon monoxidemay be produced and further shot/vr that the amount of carbon monoxidemaybe controlled by the amount of water added. l

The present invention, besides being very useful in `the production ofhydrogen and mixtures of hydrogen vand carbon monoxide for use invarious catalytic and thermal processes, is also quite useful inproducing maximum quantities of hydrogen from the hydrocarbon charged.This may be accomplished by charging the hydrocarbon as has beendescribed Vwith respect to the several iigures of the drawing to formhydrogen and deposit carbon on the catalyst. Thereafter the catalystmixture is ltreated with steam, as has been described, at a ternperatureof about 1300 F. to form hydrogen and carbon monoxide. The hydrogen andcarbon monoxide mixture may then be passed over a supported iron oxidecatalyst to convert the carbon monoxide to carbon dioxide in thepresence of additional quantities of steam. The carbon dioxide isremoved by suitable means, such as absorption in a solution of monoordiethanolamine or the like, and the purified hydrogen resultingtherefrom may be combined from-the hydrogen formed by initialdecomposition of ahydrocarbon. In other words, in this modey ofpracticing the present invention, hydrogen-is obtained not only from thehydrocarbon but also from steam by reaction with the carbon and carbonmonoxide. This is quite advantageous'in that the carbon which has beendeposited on the catalyst mixture not only is removed from the catalystmixture and the catalyst put into condition for reuse but it serves as ameans for producing additional hydrogen. .1

The presentinvention is susceptible to many variations all coming withinthe' purviewY of the-claims. It is intended that the several examplesare given by lway of illustration and not to be construed by way oflimitation.

This application contains subject matter common to an applicationentitled Treatment of Hydrocarbons, Serial No. 587,699, filed rMay 28,1956, for Prentiss S. Viles..

The nature and objects of the present invention having been completelydescribed andillustrated, what Iwish to claimV as new and useful and tosecure by Letters Patent is:

1. A method for preparing hydrogen which comprises contacting asaturated hydrocarbon having 1 to 3 carbon atoms in the molecule with acatalyst mixture of cobaltous oxide and molybdic trioxide in a mol ratioin the range of 0.1:1 to 1:0.1 at a temperature within the range of 850to 1600 F. at a pressure within the range from about 0 pound absolute toabout 1000 p.s.i.g. and at a feed rate within the range from about 1 toabout 500 volumes of hydrocarbon per volume of catalyst per hour to forma product containing a substantial amount of hydrogen and recoveringsaid product. v

2. A method in accordance with claim 1 in which water is admixed withthe hydrocarbon.

3. A method in accordance with claim 1 in which the catalyst mixture issupported.

4. A method in accordance with claim 1 in which the hydrocarbon ismethane.

5. A method in accordance with claim l in which the hydrocarbon isnatural gas.

6. A method in accordance with claim 1 in which the hydrocarbon isethane.

7. A method for preparing hydrogen which comprises forming a bed ofsupported catalyst mixture of cobaltous oxide and molybdic trioxide in amol ratio in the range of 0.1:1 to 1:0.1 in a reaction zone, contactingsaid bed with a saturated hydrocarbon having from l to 3 carbon atoms inthe molecule at a temperature within the range of 850 to 1600 F. and ata pressure within the range of 0 pound absolute to about 1000 p.s.i.g.at a space velocity in the range of about 1 to about 500` volumes ofhydrocarbon per volume of catalyst per hour to form a product containinga substantial amount of hydrogen,

and recovering said product.

8. A method for preparing hydrogen which comprises forming a suspensionof a catalyst mixture of cobaltous oxide and molybdic trioxide in a molratio in the range of 0.1:1 to 1:0.1 in a saturated hydrocarbon havingfrom 1 to 3 carbon atoms in the molecule at a temperture Within the'range of 850 to 1600 F. and at a pressure within the range of 0 poundabsolute to about 1000 p.s.i.g. at a space velocity in the range fromabout 1 to about 500 volumes of vaporized hydrocarbon per volume ofcatalyst per hour to form a product containing a substantial amount ofhydrogen, separating the product from the catalyst, and recovering saidproduct.

9. A method for preparing hydrogen which comprises contacting asaturated hydrocarbon having from 1 to 3 5 carbon atoms in the moleculewith a catalyst mixture of cobaltous oxide and molybdic trioxide in amol ratio in the range of 0.1:1 to 1:0.1 at a temperature within therange of about 850 to 1600 F. and at a pressure within therange fromabout 0 pound absolute to about 1000 p.s.i.g. at a space velocity in therange of about 1 to about 500 volumes of hydrocarbon per volume ofcatalyst per hour to form a product containing a substantial amount ofhydrogen, continuing the contacting operation until the cobalt molybdatecatalyst shows decreasing activity for forming said hydrogen product,interrupting the contacting of the hydrocarbon with said catalyst,contacting the catalyst with water vapor at a temperature within therange of about 850 to about 1600 F. for a sucient length of time toremove carbonaceous bodies deposited on said catalyst and to regeneratesaid catalyst, and then resuming the contacting of said hydrocarbon withsaid regenerated catalyst.

10. A method for preparing hydrogen which comprises contacting asataurated hydrocarbon having from 1 to 3 carbon atoms in the moleculein the presence of Water vapor with a catalyst mixture of cobaltousoxide and molybdic trioXide in a mol ratio in the range of 0.1:1 to1:0.1 at a temperature Within the range of about 850 to about 1600 F.and at a pressure Within the range of 0 pound absolute to about 1000p.s.i.g. and at a space velocity within the range of 1 to about 500volumes 12 of hydrocarbon per volume of catalyst per hour to form aproduct containing a substantial amount of hydrogen and unreactedhydrocarbon, and contacting at least the unreacted hydrocarbon in saidproduct again with said cobalt molybdate catalyst.

11. A method in accordance with claim 1 in which the hydrocarbon ispropane.

References Cited in the le of this patent UNITED STATES PATENTS1,497,751 Hopkinson June 17,

1,868,919 Schmidt et al. July 26, 1932 2,392,738 Holder et al. Jan. 8,1946 2,393,288 Byrns Jan. 22, 1946 2,425,754 Murphree et al. Aug.'19,1947 2,513,022 Helmers et al. fJune 27, 1950 2,573,726 Porter et a1.Nov. 6, 1951 2,707,147 Shapleigh Apr. 26, 1955 2,800,395 Bond v July 23,1957,

1. A METHOD FOR PREPARING HYDROGEN WHICH COMPRISES CONTACTING ASATURATED HYDROCARBON HAVING 1 TO 3 CARBON ATOMS IN THE MOLECULE WITH ACATALYST MIXTURE OF COBALTOUS OXIDE AND MOLYBDIC TRIOXIDE IN A MOL RATIOIN THE RANGE OF 0.1:1 TO 1:0.1 AT A TEMPERATURE WITHIN THE RANGE OF 850*TO 1600* F. AT A PRESSURE WITHIN THE RANGE FROM ABOUT 0 POUND ABSOLUTETO ABOUT 1000 P.S.I.G. AND AT A FEED RATE WITHIN THE RANGE FROM ABOUT 1TO ABOUT 500 VOLUMES OF HYDROCARBON PER VOLUME OF CATALYST PER HOUR TOFORM A PRODUCT CONTAINING A SUBSTANTIAL AMOUNT OF HYDROGEN ANDRECOVERING SAID PRODUCT.